Soluble copolymers



United States Patent o SOLUBLE COPOLYMERS 2,817,651 Patented Dec 24,-

tanol, dimethyl formarnide, xylene-butanol mixtures, hot xylene and acetone.

The copolymers of this invention are prepared by reacting together an unsaturated alcohol taken from the 5 group consisting of allyl and methallyl alcohol and mix- Earl C. Chapin, Springfield, and Richard F. Smith, tures thereof with one or more allryl esters of acrylic acid Ludlow, Mass., assignors to Monsanto Chemical Comor methacrylic acid in which the alkyl group may conpany, St. Louis, M-, a corporation of D lawa tain from 1-20 carbon atoms. The reaction is carried out by mixing the monomers and heating the mixture at No sefia l 133 3: 5 my 17, 1955 50-250 C. for from -75 minutes under autogenous I pressure in a substantially oxygen free atmosphere. The 10 Claims. (Cl. Mil-86.1) reaction is generally carried out without a solvent but a relatively inert organic solvent such as xylene or benzene may be used if desired. This invention relates to copolymers of unsaturated 5 The reaction can be initiated thermally particularly in alcohols with acrylic esters. More particularly the inventhe 200250 C. range but it is preferable to use a free tiou relates to a process for preparing such copolymers in radical polymerization initiator such as di-tertiarybutyl organic solvent soluble fofrm. d l h 1 h peroxide, tertiarybutyl perbenzoate, pinacolone peroxide, Copolymers prepared rom unsaturate a co 0 s sue etc. The amount of free radical initiator will depend on as allyl alcohol and acrylic esters such as ethyl acrylate the temperature conditions used and may vary from none by conventional processes of heating mixtures of the at the higher temperatures to as much as 5% by weight monomers With Oxygen PemXide i y h l p i based on the Weight of the monomer mixture at the lower tures up to 100 C., have a relativey hig mo ecu ar temperature Weight and are dimc1{1t1y Soluble in Organic l q due The reaction should be carried out in a closed reaction to extensive cl'osslinkmg duflllg the copolymefllatwn vessel under autogenous pressure although it is possible act(1)on. b t f th f t d 1 bl go pugaddehd pressure for;l the system without materially ue 0 yec 0 1s inven 101' 13 O pIOVl e SO H e (20- stur mg! e course 0 t e reaction P y of unsaturated alcqhols and acryllc esters- The products of the polymerization reaction are syrupy A further Object is to PTOWde a Process for P Y P liquids which comprise the copolymer dissolved in unreizing unsaturated alcohols with acrylic esters to prov de acted monomer and solvent if a solvent is used The F P Y F of low molecular Welght and good solublmy unreacted monomer and solvent are removed by vacuum 111 organ: solYentsdistillation at temperatures from l00250 C. The co- Another oblect P thls Invention 15 to pmvltle 8 1 polymers thus recovered range from brittle solids such as ess for copolymeriz ng unsaturated alcohols with acrylic the copolymers of Examples IV and VI to soft pastes f Wh1ch mlmmlzes cmsshnkmg durmg the Polymer such as the copolymers of Examples VII and IX. If due anon reactlon' d b 1 care is taken in the purity of the raw materials and in the These and i i f i are y cope ymerzmg handling thereof in the reaction and purification steps, gi g g g g i g zggg i 3222;? tempera mes the copolymers are clear and substantially colorless. They In the following illustrative examples, parts are by 40 are soluble in alcohols, ketones, hot aromatic hydrocarhens, and mixtures of the alcohols and the aromatic h weight. y

drocarbons. The copolymers contain from 140% of Example I unsaturated alcohol by weight Mix together 35 Parts fi l acrylate, 15 Pa of allyl The copolymers of this invention are particularly usealcohol and 0.2 part of dl-tertiarybutyl peroxide. Heat f l in coating Compositions as the major resin compo the mixture 1n a closed reaction vessel in the substantlal nent thereof together with minor amounts of other com f F of oxygen at prloduct ventional coating resins such as the alkyd resins and g ggj f gi gf g f f iz gg g ggg i g gi the phenol, urea or melamine-formaldehyde condensation I 1 a uum distillation at 110 C. to obtain a clear colorless 22 3555 g i f is g g sg gg 2:23; g f gi soft solid soluble in butanol, methanol, acetone, dimethg p I 5 yl formamide, xylene-butanol mixtures and hot xylene. mg resms are ma malor amount n a ii -i e The copolymer contains about 4.4% hydroxyl groups by F Y F of thls mventlml may m weight mg 011 acids to produce resins which Wlll air-dry.

Prepare a series of copolymers under conditions sub- 55 foregPing gf l i l l pli mi n as i E l I using 1% b i ht f ii. are 1 ustrat ve o t is invention ant 1t 1s o vious t at tertiarybutyl peroxide as polymerization initiator with the y Vaflailons y 135 made Wlthln the P 1t and scoPe following reaction mixtures. thereof- Example II III IV V VI VII VIII IX Allyl Alcohol 30 ""56 200 lgo 30 2 153 in e0 0 30 0 glfit'egmlf fiimm so 45 38.5 28.3 57.1 42 21.3 AllylAlcoholInCopolymer, percent- 23 32 7.15 15.1 5.8 6.15 9.5 2.0

In the table the various monomers are given in parts by What is claimed is: weight 7 1. An organic solvent-soluble binary copolymer of an All of the products represented by the formulae in the table are soluble in alcohols such as methanol and buunsaturated alcohol and an acrylic ester, the unsaturated alcohol constituting from 1-40% by weight of the copolya rncr, said unsaturated alcohol being taken from the group consisting of allyl alcohol, methallyl alcohol and mixtures thereof and said acrylic ester being a member of the group consisting of alkyl esters of acrylic and alkyl esters of methacrylic acids and mixtures thereof, the alkyl groups in said esters containing from 1-4 carbon atoms.

2. A copolymer as in claim 1 wherein the alcohol is allyl alcohol.

3. A copolyrner as in claim 1 wherein the acrylic ester is ethyl acrylate.

4. A copolymer as in claim 1 wherein the acrylic ester is butyl methacrylate.

5. A copolymer as in claim 1 wherein the acrylic ester is methyl rnethacrylate.

6. A process for preparing an organic solvent-soluble binary copolymer of an unsaturated alcohol and an acrylic ester which comprises mixing the monomers together and heating the mixture at 150250 C. for from l775 minutes under autogenous pressure in a substantially oxygen-- free atmosphere, said unsaturated alcohol being a member of the group consisting of allyl alcohol, methallyl alcohol and mixtures thereof, said acrylic ester being a member of the group consisting of alkyl esters of acrylic acid, alkyl esters of methacrylic acid and mixtures thereof, said alkyl groups containing from 14 carbon atoms, said copolymers containing l-40% unsaturated alcohol by weight.

7. A process as in claim 6 wherein the unsaturated alcohol is allyl alcohol.

8. A process as in claim 6 wherein the acrylic ester is ethyl acrylate.

9. A process as in claim 6 wherein the acrylic ester is methyl methacrylate.

10. A process as in claim 6 wherein the acrylic ester is butyl methacrylate.

Neher Mar. 11, 1941 Snyder May 11, 1948 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,817,651 December 24, 1957 Earl C. Chapin et a1.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction andthat the said Letters Patent should read as corrected below.

Column 3, line 18, for "17-75" read 15-75 Signed and sealed this 25th day of February 1958.

(SEAL) gAttest: KARL Ho AXLINE ROBERT 0.. WATSON 1 Commissioner of Paten- Attesting Officer 

1. AN ORGANIC SOLVENT-SOLUBLE BINARY COPOLYMER OF AN UNSATURATED ALCOHOL AND AN ACRYLIC ESTER, THE UNSATURATED ALCOHOL CONSTITUTING FROM 1-40% BY WEIGHT OF THE COPOLYMER, SAID UNSATURATED ALCOHOL BEING TAKEN FROM THE GROUP CONSISTING OF ALLYL ALCOHOL, METHALLYL ALCOHOL AND MIXTURES THEREOF AND SAID ACRYLIC ESTER BEING A MEMBER OF THE GROUP CONSISTING OF ALKYL ESTERS OF ACRYLIC AND ALKYL ESTERS OF METHACRYLIC ACIDS AND MIXTURES THEREOF, THE ALKYL GROUPS IN SAID ESTERS CONTAINING FROM 1-4 CARBON ATOMS. 